CN102271811A - Method for producing oxidized compound - Google Patents

Abstract

A method for producing an oxidized compound according to the present invention comprises reacting an organic compound with an oxidizing agent in the presence of titanosilicate (I) or a silylated form thereof, the titanosilicate (I) being obtained by contacting titanosilicate (II) with a structure-directing agent, and the titanosilicate (II) having an X-ray diffraction pattern reproduced in the form of interplanar spacings d of 1.24 0.08 nm, 1.08 0.03 nm, 0.9 0.03 nm, 0.6 0.03 nm, 0.39 0.01 nm and 0.34 0.01 nm.

Description

Process for the preparation of oxidized compounds

technical field

The present invention relates to a process for the preparation of oxidized compounds.

Background technique

In terms of methods for producing oxidized compounds using titanosilicate catalysts, Non-Patent Documents 1 and 2 disclose methods involving epoxidation of cyclopentene by reaction with hydrogen peroxide in the presence of a Ti-MWW precursor catalyst , wherein the catalyst was obtained by acid treatment of titanium-containing layered compounds with 2M HNO ₃ . Patent Document 1 discloses a production method of propylene oxide comprising reacting propylene with hydrogen peroxide in the presence of the same catalyst as described above.

Non-Patent Document 3 discloses a Ti-MWW precursor containing 13.5wt% to 14.2wt% of organic amines, which is obtained by: mixing Ti-MWW, piperidine and water; washing the obtained compound with water; The compound was dried overnight at . The Si/N ratio of this Ti-MWW precursor is calculated to be 8.5 to 8.6 by the ICP (Si/Ti, Si/B) described therein, and by CHN analysis, thus having a higher ratio than the Ti - Higher nitrogen content of MWW precursors.

Literature list

Non-Patent Document 1: Catalysis Today 117 (2006) 199-205

Non-Patent Document 2: 91st CATSJ Meeting Abstracts: No. 1B07 (2003)

Non-Patent Document 3: Journal of Physical Chemistry C, Vol. 112 No. 15, 2008

Patent Document 1: Japanese Patent Laid-Open No. 2005-262164.

Contents of the invention

It is an object of the present application to provide new processes for the preparation of oxidic compounds and titanosilicates.

Specifically, this application relates to the following inventions.

[1] A method of producing an oxidized compound comprising reacting an organic compound with an oxidizing agent in the presence of titanosilicate (I) or its silylated form by making titanosilicate (II) obtained by contacting with a structure directing agent, said titanosilicate (II) having an X-ray diffraction pattern in the form of the following interplanar distance d:

1.24±0.08 nm,

1.08±0.03 nm,

0.9±0.03 nm,

0.6±0.03 nm,

0.39±0.01 nm and

0.34±0.01nm.

[2] The method for producing an oxygenated compound according to [1], wherein the organic compound is an olefin compound or an aromatic compound.

[3] The method for producing an oxidized compound according to [1] or [2], wherein the molar ratio of silicon to nitrogen (Si/N ratio) of the titanosilicate (I) is 5-20 (including terminal value).

[4] The method for producing an oxidized compound according to any one of [1] to [3], wherein the ratio of the specific surface area (SH ₂ O) to the specific surface area (SN ₂ ) of the titanosilicate (I) is The ratio (SH ₂ O/SN ₂ ) was 0.7-1.5 inclusive, and the specific surface areas SH ₂ O and SN ₂ were measured by water vapor adsorption and nitrogen adsorption methods, respectively.

[5] The method for producing an oxidized compound according to any one of [1] to [4], wherein the titanosilicate (II) is a crystalline titanosilicate or Ti-MWW having a structure of MWW or MSE Precursor (a).

[6] The method for producing an oxidized compound according to any one of [1] to [5], wherein the structure directing agent is piperidine or hexamethyleneimine or a mixture thereof.

[7] The method for producing an oxidized compound according to any one of [1]-[6], wherein the contact of the titanosilicate (II) with the structure-directing agent is at 0-250°C (including at the temperature of the end value).

[8] A titanosilicate or a silylated form thereof, wherein the molar ratio of silicon to nitrogen (Si/N ratio) of the titanosilicate is 10 to 20 inclusive.

[9] The titanosilicate or a silylated form thereof according to [8], wherein the titanosilicate is obtained by contacting titanosilicate (II) with a structure-directing agent, the titanosilicate Salt (II) has an X-ray diffraction pattern in the form of the following interplanar distance d:

1.24±0.08 nm,

1.08±0.03 nm,

0.9±0.03 nm,

0.6±0.03 nm,

0.39±0.01 nm and

0.34±0.01nm.

[10] The titanosilicate or a silylated form thereof according to [9], wherein the titanosilicate (II) is a crystalline titanosilicate having a MWW or MSE structure or a Ti-MWW precursor (a).

[11] Use of the titanosilicate or a silylated form thereof according to any one of [8] to [10] as a catalyst in a process for producing an oxidized compound.

[12] A catalyst for an oxidation reaction of an organic compound comprising titanosilicate (I) or a silylated form thereof obtained by combining titanosilicate (II) with the structure obtained by directing agent contact, the titanosilicate (II) has an X-ray diffraction pattern expressed in the form of the following interplanar distance d:

1.24±0.08 nm,

1.08±0.03 nm,

0.9±0.03 nm,

0.6±0.03 nm,

0.39±0.01 nm and

0.34±0.01nm.

[13] The method for producing an oxidized compound according to any one of [1] to [7], wherein the oxidizing agent is oxygen or a peroxide.

[14] The method for producing an oxidized compound according to [13], wherein the peroxide is at least one compound selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide cumene hydroperoxide, methylcyclohexyl hydroperoxide, tetralin hydroperoxide, isobutylbenzene hydroperoxide, ethylnaphthalene hydroperoxide and peracetic acid.

[15] The method for producing an oxidized compound according to any one of [1]-[7], [13], and [14], wherein the reaction is an epoxidation reaction of an olefin compound or an epoxidation reaction of a benzene or phenol compound Hydroxylation reaction.

[16] The method for producing an oxidized compound according to any one of [1]-[7], [13], [14], and [15], wherein the reaction is an epoxidation reaction of an olefin compound, and The oxidizing agent is hydrogen peroxide.

[17] The method for producing an oxidized compound according to [16], wherein the oxidizing agent is hydrogen peroxide synthesized in the same reaction system as the epoxidation reaction of the olefin compound.

[18] The method for producing an oxidized compound according to any one of [1]-[7], [13], [14], [15], [16], and [17], wherein the reaction is carried out in an organic carried out in the presence of a solvent selected from alcohols, ketones, nitriles, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, esters and mixtures thereof.

[19] The method for producing an oxidized compound according to [18], wherein the organic solvent is acetonitrile or tert-butanol.

The production method of the present invention is used as a method for producing oxidized compounds. The titanosilicate (I) is used as a catalyst for oxidation reactions of organic compounds.

Description of drawings

Figure 1 is a graph showing the X-ray diffraction pattern of Catalyst A;

Figure 2 is a graph showing the X-ray diffraction pattern of Catalyst B;

Figure 3 is a graph showing the X-ray diffraction pattern of Catalyst C;

Figure 4 is a graph showing the X-ray diffraction pattern of Catalyst D;

Figure 5 is a graph showing the X-ray diffraction pattern of Catalyst E;

Figure 6 is a graph showing the X-ray diffraction pattern of Catalyst F;

Figure 7 is a graph showing the X-ray diffraction pattern of Catalyst G;

Figure 8 is a graph showing the X-ray diffraction pattern of Catalyst H;

Figure 9 is a graph showing the X-ray diffraction pattern of Catalyst 1;

Figure 10 is a graph showing the X-ray diffraction pattern of Catalyst J;

Figure 11 is a graph showing the X-ray diffraction pattern of Catalyst K;

Figure 12 is a graph showing the X-ray diffraction pattern of Catalyst L;

Figure 13 is a graph showing the X-ray diffraction pattern of catalyst M;

Figure 14 is a graph showing the X-ray diffraction pattern of solid product 1;

Figure 15 is a graph showing the X-ray diffraction pattern of solid product 2;

Figure 16 is a graph showing the X-ray diffraction pattern of solid product 3;

Figure 17 is a graph showing the X-ray diffraction pattern of solid product 4;

Figure 18 is a graph showing the X-ray diffraction pattern of powder b3;

Figure 19 is a graph showing the X-ray diffraction pattern of powder f2;

Figure 20 is a graph showing the X-ray diffraction pattern of the solid product g6;

Figure 21 is a graph showing the X-ray diffraction pattern of solid product h3;

Figure 22 is a graph showing the X-ray diffraction pattern of solid product i3; and

Figure 23 is a graph showing the X-ray diffraction pattern of powder j2;

Fig. 24 is a diagram showing an X-ray diffraction pattern of powder n2.

Detailed ways

The process of the present invention for the preparation of oxidized compounds comprises reacting an organic compound with an oxidizing agent in the presence of titanosilicate (I) or its silylated form by making titanosilicate (II) obtained by contacting with a structure directing agent, said titanosilicate (II) having an X-ray diffraction pattern in the form of the following interplanar distance d:

1.24±0.08 nm,

1.08±0.03 nm,

0.9±0.03 nm,

0.6±0.03 nm,

0.39±0.01 nm and

0.34±0.01nm.

Titanosilicate is a generic name for a silicate having tetracoordinated Ti. The titanosilicates described herein can be determined to have a UV-Vis absorption spectrum in the wavelength range of 200 nm to 500 nm having a maximum absorption peak in the wavelength range of 220 ± 10 nm (see, e.g., Chemical Communications 1026-1027, (2002)). The UV-vis absorption spectrum can be measured by diffuse reflectance using a UV-vis spectrophotometer equipped with a diffuse reflectance accessory.

Ti-MWW refers to crystalline titanosilicates with MWW structure. The MWW structure is a molecular sieve structure represented by a structure code assigned by the International Zeolite Association (IZA). This structure has a supercage (0.7 × 0.7 × 1.8 nm) with pores composed of oxygen 10-membered rings and openings composed of oxygen 10-membered rings and hemispherical sides with openings composed of oxygen 12-membered rings pocket.

The titanosilicate (I) is obtained by contacting the titanosilicate (II) with a structure-directing agent, so it is presumed to some extent that it has pores that are derived from the titanosilicate ( The structure directing agent is contained in the porous structure of II). The pore structure like titanosilicate (I) is confirmed by the X-ray diffraction pattern described below.

Furthermore, said titanosilicate (I) was obtained by contacting titanosilicate (II) with a structure-directing agent without a calcination step, so the X-ray diffraction pattern differs from that of the MWW structure, as follows mentioned. The titanosilicate (I) exhibits excellent activity as a catalyst for oxidation reactions of organic compounds.

In the ultraviolet-visible absorption spectrum measured by a diffuse reflectance method (baseline standard: Spectralon) with an ultraviolet-visible spectrophotometer, the titanosilicate (I) has an absorption peak in the wavelength range of 210nm-230nm.

The titanosilicate (I) generally exhibits the following X-ray diffraction pattern:

distance between faces d

1.24 ± 0.08 nm (12.4 ± 0.8 Å)

1.08 ± 0.03 nm (10.8 ± 0.3 Å)

0.9 ± 0.03 nm (9 ± 0.3 Å)

0.6 ± 0.03 nm (6 ± 0.3 Å)

0.39 ± 0.01 nm (3.9 ± 0.1 Å)

0.34 ± 0.01 nm (3.4 ± 0.1 Å)

The titanosilicate (I) further exhibits the following relationship: in the X-ray diffraction pattern, the intensity ratio X ¹ /X ² (X ¹ /X ² = the peak intensity X ¹ at the plane distance 9 ± 0.3 Å and the plane distance The peak intensity at 3.4 ± 0.1 Å ^x ratio) is greater than 0 and is 0.4 or less, preferably 0.05-0.4.

In the present specification, the X-ray diffraction pattern may be measured by using an X-ray diffractometer by utilizing radiation of copper Kα X-rays.

The molar ratio of silicon to nitrogen (Si/N ratio) of the titanosilicate (I) is preferably, but not specifically limited to, 5-20 inclusive.

The lower limit of the Si/N ratio is more preferably 8, even more preferably 10; the upper limit of the Si/N ratio is more preferably 35, even more preferably 18, particularly preferably 16.

The titanosilicate (I) with Si/N ratio in this range can exhibit more excellent catalytic activity. One aspect of the invention comprises titanosilicates or silylated forms thereof, wherein said titanosilicates have a silicon to nitrogen molar ratio (Si/N ratio) of 10-20 inclusive.

The titanosilicate and its silylated form of the present invention can be prepared by the same methods as the titanosilicate (I) and its silylated form, respectively.

The molar ratio of silicon to nitrogen (Si/N ratio) was determined by elemental analysis of the samples. The elemental analysis can be performed by conventional methods as follows: Ti (titanium), Si (silicon) and B (boron) can be determined by alkali fusion, dissolved in nitric acid and ICP emission spectroscopy; N (nitrogen) can be determined by oxygen cycle combustion And TCD detection system to determine.

The ratio (SH ₂ O/SN ₂ ) of the specific surface area (SH ₂ O) to the specific surface area (SN ₂ ) of the titanosilicate (I) is usually 0.7 or greater, preferably 0.8 or greater; the SH The upper limit of the ₂ O/SN ₂ ratio is usually 1.5, preferably 1.3.

In the present invention, the specific surface area SN ₂ is determined by degassing a sample at 150° C., measuring the degassed sample by a nitrogen adsorption method, and calculating its area by a BET method. The specific surface area SH ₂ O is determined by degassing the sample at 150° C., measuring the degassed sample by water vapor adsorption at an adsorption temperature of 298 K, and calculating the area by the BET method.

The titanosilicate (I) is obtained by contacting the titanosilicate (II) with the structure directing agent.

The silylated form of the titanosilicate (I) is obtained by catalyzing the titanosilicate (I) with a silylating agent such as 1,1,1,3,3,3-hexamethyldisilazane I) obtained by silylation.

In the specification of the present invention, the structure directing agent refers to an organic compound used to form a zeolite structure. The structure directing agent can form a precursor of the zeolite structure by organizing polysilicic acid or polymetasilicate ions into a topology around it (see Science and Engineering of Zeolite, pp. 33-34, 2000, Kodansha Scientific Ltd).

Any nitrogen-containing compound that can form a zeolite having a MWW structure can be used as the structure-directing agent without particular limitation. Examples of the structure-directing agent include: organic amines such as piperidine and hexamethyleneimine, etc., and quaternary ammonium salts such as N,N,N-trimethyl-1-adamantanammonium (adamantanammonium) salt ( N,N,N-trimethyl-1-adamantyl ammonium hydroxide, N,N,N-trimethyl-1-adamantyl ammonium iodide, etc.) and Chemistry Letters 916-917 (2007) octyltrimethylammonium salts (octyltrimethylammonium hydroxide, octyltrimethylammonium bromide, etc.). These compounds may be used alone or as a mixture of two or more compounds in any ratio.

The structure directing agent is preferably piperidine or hexamethyleneimine.

In the preparation of the titanosilicate (I), relative to 1 part by weight of the titanosilicate (II), the lower limit of the amount of the structure directing agent is usually 0.01 parts by weight, preferably 0.1 parts by weight, more preferably It is preferably 1 part by weight, even more preferably 2 parts by weight; relative to 1 part by weight of titanosilicate (II), the upper limit of the amount of the structure directing agent is preferably 100 parts by weight, preferably 50 parts by weight, more preferably 20 parts by weight, even more preferably 15 parts by weight, especially preferably 10 parts by weight.

Using the structure directing agent in an amount within this range, the titanosilicate (I) can be easily prepared.

The contact of the titanosilicate (II) and the structure directing agent can be carried out by the following method: the titanosilicate (II) and the structure directing agent are placed in a closed container such as an autoclave and passed heat to pressurize; or mix the titanosilicate (II) and the structure directing agent in a vessel such as a glass flask in the atmosphere with or without stirring.

In terms of the lower limit, the contacting is carried out at a temperature of preferably 0°C, more preferably 20°C, even more preferably 50°C, especially preferably 100°C; in terms of the upper limit, the contacting is carried out at a temperature of about 250°C, preferably 200°C, It is more preferably carried out at a temperature of 180°C.

The contacting is performed under any pressure without specific limitation, and is generally performed at about 0-10 MPa in gauge pressure. The titanosilicate (I) obtained by said contacting is usually isolated by filtration. If necessary, the isolated titanosilicate (I) may be post-treated, such as washing and drying. It is speculated that this post-treatment can also adjust the amount of said structure-directing agent in the titanosilicate (I) obtained.

In the present invention, titanosilicate (I) is preferably obtained by further washing after contacting. It is presumed that this washing not only increases the purity of the titanosilicate (I) obtained, but also regulates the amount of structural orientation present in the titanosilicate (I). The washing can be performed by appropriately adjusting the usage amount, pH value, etc. of the washing liquid, if necessary. The washing is preferably performed with water as the washing solution, more preferably until the pH of the washing solution is 7-11. When drying is performed after contact, its conditions including temperature can be appropriately set within a range not to impair the properties of the titanosilicate (I) shown below.

Herein, the titanosilicate (I) is converted into a MWW structure by calcination and is thus classified as a Ti-MWW precursor.

Examples of the titanosilicate (II) include crystalline titanosilicate having a MWW or MSE structure, Ti-MWW precursor (a) and Ti-YNU-1.

Examples of Ti-YNU-1 include Angewandte Chemie Ti-YNU-1 described in International Edition 43, 236-240, (2004).

Examples of the crystalline titanosilicate having a MWW structure include Ti-MWW described in Japanese Patent Laid-Open No. 2003-327425. Examples of the crystalline titanosilicate having an MSE structure include Ti-MCM-68 described in Japanese Patent Laid-Open No. 2008-50186.

In the description of the present invention, the Ti-MWW precursor refers to titanosilicate having a layered structure. The Ti-MWW precursor exhibits Ti-MWW characteristics through calcination. The calcination will be described below.

Any layered form of titanosilicate converted to Ti-MWW by calcination can be used as the Ti-MWW precursor (a), without specific limitation. The Ti-MWW precursor (a) has a molar ratio of silicon to nitrogen (Si/N ratio) of 21 or more. The titanosilicate (I) can also be used as Ti-MWW precursor (a).

Examples of the Ti-MWW precursor (a) include Ti-MWW precursors described in Japanese Patent Laid-Open No. 2005-262164.

The titanosilicate (II) is preferably a crystalline titanosilicate with a MWW or MSE structure, or a Ti-MWW precursor (a), more preferably a Ti-MWW with a MWW structure, or a Ti-MWW precursor ( a).

The titanosilicate (II) can be prepared by methods well known in the art such as those described in the literature. Said crystalline titanosilicate with MWW structure can also be prepared, for example, by calcining the Ti-MWW precursor (a).

Examples of typical methods for producing the Ti-MWW precursor (a) include the following first to third aspects.

The first aspect is a production method comprising steps 1 and 2 described below.

step 1

In step 1, a compound containing a structure directing agent, a compound containing an element belonging to Group 13 of the periodic table (hereinafter, the compound is referred to as a "group 13 element-containing compound"), a silicon-containing compound, a titanium-containing compound, and Mixtures of water to obtain layered compounds.

step 2

In step 2, the layered compound obtained in step 1 is subjected to acid treatment to obtain Ti-MWW precursor (a).

Herein, the layered compound is referred to as an as-synthesized sample. This sample was directly converted into zeolites with MWW structure by calcination. However, in the layered compound, the ultraviolet-visible absorption spectrum in the wavelength range of 200nm-500nm does not have the maximum absorption peak in the wavelength range of 220±10nm. Thus, the layered compounds are not titanosilicates and are clearly distinguished from Ti-MWW precursors (see for example Chemistry Letters 774-775 (2000)).

Examples of the structure-directing agent in step 1 include the same compounds as those used in the preparation of titanosilicate (I). These compounds may be used alone or as a mixture of two or more thereof in any ratio.

The structure directing agent is preferably piperidine or hexamethyleneimine.

In the mixture in step 1, the amount of the structure directing agent is preferably 0.1-5 mol, more preferably 0.5-3 mol relative to 1 mol of silicon in the silicon-containing compound.

Examples of the Group 13 element-containing compound include boron-containing, aluminum-containing, and gallium-containing compounds. Boron-containing compounds are preferred.

Examples of the boron-containing compound include boric acid, borate, boron oxide, boron halide, and trialkylboron compounds containing an alkyl group having 1 to 4 carbon atoms. In particular, boric acid is preferred.

Examples of the aluminum-containing compound include sodium aluminate. Examples of the gallium-containing compound include gallium oxide.

In the mixture in step 1, the amount of the compound containing Group 13 elements is preferably 0.01-10 mol, more preferably 0.1-5 mol relative to 1 mol of silicon in the silicon-containing compound.

Examples of the silicon-containing compound include silicic acid, silicate, silicon oxide, silicon halide, fumed silica compound, tetraalkyl orthosilicate, and colloidal silicon dioxide. Fumed silica compounds are preferred.

In the mixture in step 1, the proportion of water is preferably 5-200 mol, more preferably 10-50 mol relative to 1 mol of silicon in the silicon-containing compound.

Examples of the titanium-containing compound include titanium alkoxide, titanate, titanium oxide, titanium halide, titanium inorganic acid salt, and titanium organic acid salt. Titanium alkoxides are preferred.

Examples of the titanium alkoxide include compounds containing an alkoxy group having 1 to 4 carbon atoms, such as tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium.

Examples of the titanium organic acid salt include titanium acetate. Examples of the titanium inorganic acid salt include titanium nitrate, titanium sulfate, titanium phosphate and titanium perchlorate. Examples of the titanium halide include titanium tetrachloride. Examples of the titanium oxide include titanium dioxide.

In the mixture in step 1, the amount of the titanium-containing compound is usually in the range of preferably 0.005-0.1 mol, more preferably 0.01-0.05 mol relative to 1 mol of silicon in the silicon-containing compound.

The heating step in step 1 is preferably carried out by placing the mixture in a closed container such as an autoclave, subjecting to hydrothermal synthesis conditions including pressurization by heating (see, for example, Chemistry Letters 774-775 (2000)). The heating step is carried out at a temperature preferably in the range of 110°C to 200°C, more preferably in the range of 120°C to 180°C. The mixture thus heated is usually separated into solid and liquid components by filtration. The remaining material in the thus heated mixture was filtered off. Furthermore, the solid component is washed with water or the like and dried with heat to obtain the layered compound. In this case, it is preferable to wash the solid component until the pH of the washing liquid is 7-11. The heat drying is preferably carried out at a temperature of about 0°C to 100°C until the weight loss of the solid component is no longer seen.

Next, step 2 will be described.

In step 2, the layered compound obtained in step 1 is subjected to acid treatment to obtain Ti-MWW precursor (a).

"Acid treatment" as used herein refers to contacting with an acid and in particular to contacting the compound to be treated with an acid-containing solution or the acid itself. The contacting may be performed by any method without limitation, and may be performed by spraying or applying an acid or an acid solution to the compound to be treated; or immersing the compound to be treated in the acid or an acid solution. A method in which the compound to be treated is immersed in an acid or an acid solution is preferred.

The acid used in the acid treatment may be an inorganic acid or an organic acid. Examples of inorganic acids include nitric acid, hydrochloric acid, sulfuric acid, perchloric acid, and fluorosulfonic acid. Examples of organic acids include formic acid, acetic acid, propionic acid and tartaric acid. In the acid treatment, these acids may be used alone or in combination of two or more thereof.

The acid solution can be prepared, for example, by dissolving an organic or inorganic acid salt in a solvent. Examples of the solvent include water, alcohols, ethers, esters, ketones and mixtures thereof. In particular, water is preferred.

The acid is used in any concentration without particular limitation, and is usually used in the range of 0.01M-20M (M:mol/l). The concentration of the mineral acid is preferably 1M-5M.

The contacting of the layered compound with the acid is performed at any temperature without limitation, and is generally performed at 0°C to 200°C, preferably at 50°C to 180°C, more preferably at 60°C to 150°C.

Said second aspect of preparing said Ti-MWW precursor (a) is a method comprising steps I-IV as described below.

Step I

In step I, a mixture comprising a structure directing agent, a group 13 element-containing compound, a silicon-containing compound and water is heated to obtain a solid product a.

Step II

In step II, the solid product a is acid-treated to obtain solid product b.

Step III

In step III, a structure directing agent, a titanium-containing compound and water are added to said solid product b, and the resulting mixture is heated to obtain a solid product c.

Step IV

In step IV, the solid product c is subjected to acid treatment to obtain Ti-MWW precursor (a).

Examples of the structure-directing agent in step I include the same compounds as those used in the preparation of titanosilicate (I). The structure directing agent is preferably piperidine or hexamethyleneimine. These compounds may be used alone or in the form of a mixture of two or more thereof in any ratio.

In the mixture in step 1, the amount of the structure directing agent is preferably 0.1-5 mol, more preferably 0.5-3 mol relative to 1 mol of silicon in the silicon-containing compound.

Examples of the Group 13 element-containing compound and the silicon-containing compound described in Step I include the same compounds as those used in the preparation of the first aspect, respectively.

In the mixture in step 1, the amount of the compound containing Group 13 elements is preferably 0.01-10 mol, more preferably 0.1-5 mol relative to 1 mol of silicon in the silicon-containing compound.

In the mixture in step 1, the proportion of water is preferably 5-200 mol, more preferably 10-50 mol relative to 1 mol of silicon in the silicon-containing compound.

The heating step described in step I can be performed in the same manner as in step 1 of the first aspect.

Alternatively, step I-2 shown below can also be carried out between said steps I and II. In this case, the solid product a1 obtained in Step I-2 was used in Step II instead of the solid product a obtained in Step I.

Step I-2

In step I-2, the solid product a is calcined.

Calcination is a method of treating minerals at high temperatures for the purpose of chemical reaction, sintering or thermal decomposition such as dehydrative condensation (see Chemical Dictionary, KYORITSU SHUPPAN CO., LTD, 1960) and is generally different from drying for the purpose of removing moisture. In the present invention, the purpose of the calcination is to perform dehydration condensation between the layers of the layered compound. The calcination is performed in a non-liquid phase, so it differs from heat treatment in a liquid phase. Calcination for the preparation of Ti-MWW precursor (a) may not result in complete dehydration condensation.

The calcination can be performed under conditions known in the art, and can be performed in an open system or a gas flow system. The calcination is most easily carried out in the presence of a gas. Or alternatively, the calcination may be performed by introducing oxygen thereinto after heating to a predetermined temperature under an atmosphere of an inert gas such as nitrogen.

In the specification of the present invention, the calcination temperature range is preferably higher than 200°C and 1000°C or lower, more preferably 300°C-650°C. Calcination at too low a temperature may take a very long time to achieve the goal. In contrast, calcination at too high a temperature may lead to structural damage.

Next, Step II will be described. In step II, the solid product a or a1 is subjected to acid treatment to obtain solid product b. The acid treatment in step II can be performed in the same manner as in the first aspect.

Alternatively, step II-2 shown below can also be carried out between steps II and III. In this case, the solid product b1 obtained in step II-2 was used in step III instead of solid product b.

Step II-2

The step of calcining solid product b

This step can be performed under the same conditions as in step I-2.

Step III will be described next. In step III, the structure directing agent, the titanium-containing compound and water are added to the solid product b or b1, and the resulting mixture is heated to obtain the solid product c.

Examples of the structure directing agent and the titanium-containing compound in Step III include the same compounds as used in the first aspect, respectively. These compounds may be used alone or as a mixture of two or more thereof in any ratio.

In the mixture of step III, the amount of the structure directing agent is preferably 0.1-5 mol, more preferably 0.5-3 mol relative to 1 mol of silicon in the solid product b or b1.

In the mixture of step III, the amount of the titanium-containing compound is usually in the range of preferably 0.005-0.1 mol, more preferably 0.01-0.05 mol relative to 1 mol of silicon in the solid product b or b1.

In the mixture of step III, the proportion of water added to the solid product b or b1 is preferably 5-200 mol, more preferably 10-50 mol relative to 1 mol of silicon in the solid product b.

The heating step described in step III can be performed in the same manner as in the first aspect.

Next, Step IV will be described. In step IV, the solid product c is subjected to acid treatment to obtain Ti-MWW precursor (a).

The acid treatment described in step IV can be performed in the same manner as in the first aspect.

A third aspect for preparing said Ti-MWW precursor (a) is a method comprising steps A and B described below.

Step A

In step A, a mixture comprising a structure directing agent, a Group 13 element-containing compound, a silicon-containing compound, a titanium-containing compound and water is heated to obtain layered compound i.

Step B

In step B, the layered compound i is contacted with a titanium-containing compound and a mineral acid to obtain a Ti-MWW precursor (a).

The structure directing agent, the Group 13 element-containing compound, the silicon-containing compound, and the titanium-containing compound in step A include the same compounds as those used in the first aspect, respectively.

In the mixture in step A, the amounts of the structure directing agent, the group 13 element-containing compound, the silicon-containing compound and the titanium-containing compound are the same as those in step 1 of the first aspect.

The heating step described in step A can be performed in the same manner as in step 1.

Step A-2 shown below can also be carried out instead of step A. In this case, the solid product a obtained in step A-2 is used in step B instead of the layered compound i.

Step A-2

In step A-2, a mixture comprising the structure directing agent, the Group 13 element-containing compound, the silicon-containing compound and water is heated to obtain a solid product a.

The step A-2 can be carried out in the same manner as step I in the second aspect.

Next, Step B will be described. In step B, said layered compound i or said solid product a is contacted with a titanium-containing compound and a mineral acid to obtain a Ti-MWW precursor (a).

Examples of the inorganic acid in step B include sulfuric acid, hydrochloric acid, nitric acid, perchloric acid, fluorosulfonic acid and mixtures thereof. Nitric acid, perchloric acid, fluorosulfonic acid and mixtures thereof are preferred. When the acid is used in the form of a solution, examples of its solvent include water, alcohol, ether, ester and ketone. In particular, water is preferred. The inorganic acid is used in any concentration without particular limitation, and is usually used in the range of 0.01M-20M (M:mol/l). The concentration of the inorganic acid is preferably 1M-5M.

Examples of the titanium-containing compound described in step B include the same compounds as those used in step I. The amount of the titanium-containing compound is usually 0.001-10 parts by weight, preferably 0.01-2 parts by weight relative to 1 part by weight of layered compound i or solid product a.

The layered compound i or the solid product a is contacted with the titanium-containing compound and the inorganic acid usually by making the layered compound i or the solid product a with the titanium-containing compound and the inorganic acid The mixture of acids is contacted at a temperature of preferably 20°C to 150°C, more preferably 50°C to 104°C. The contacting is performed under any pressure without particular limitation, and is generally performed at about 0-10 MPa in gauge pressure.

The titanosilicate (I) and its silylated form, respectively, can be used as catalysts for oxidation reactions of organic compounds. One aspect of the present invention includes a catalyst for the oxidation reaction of an organic compound comprising said titanosilicate (I) or a silylated form thereof. The catalysts of the present invention are used in the oxidation of organic compounds, in particular, in the epoxidation of olefins.

The titanosilicate of the present invention and its silylated form, respectively, can be used as catalysts in the same manner as the titanosilicate (I) in the process for producing oxidized compounds.

In the production process of the present invention, an organic compound is reacted with an oxidizing agent in the presence of said titanosilicate (I) or a silylated form thereof.

In the present invention, the oxidizing agent refers to a compound that imparts (imparts) an oxygen atom to the organic compound.

Examples of the oxidizing agent include oxygen and peroxides. Examples of the peroxide include hydrogen peroxide and organic peroxides.

Examples of the organic peroxide include t-butyl hydroperoxide, di-t-butyl peroxide, t-amyl hydroperoxide, cumene hydroperoxide, methylcyclohexyl hydroperoxide, tetrahydronaphthalene hydroperoxide , isobutylbenzene hydroperoxide, ethylnaphthalene hydroperoxide and peracetic acid. These peroxides may also be used as a mixture of two or more thereof.

In particular, the peroxide is preferably hydrogen peroxide. In the production method, the hydrogen peroxide is used in the form of an aqueous solution containing hydrogen peroxide at a concentration of 0.0001 wt% or more and less than 100 wt%. The hydrogen peroxide may be prepared by a method known in the art or may be a commercially available product or a product prepared from oxygen and hydrogen in the presence of a noble metal in the same reaction system as the oxidation reaction.

In the present invention, the oxidizing agent can be used in an arbitrarily selected amount depending on the type of organic compound, reaction conditions, etc., and is preferably used in an amount of 0.01 parts by weight or more, more preferably 0.1 parts by weight, relative to 100 parts by weight of organic compounds. servings or more. The upper limit of the oxidizing agent is preferably 1000 parts by weight, more preferably 100 parts by weight, relative to 100 parts by weight of the organic compound.

Examples of the organic compound in the production method include aromatic compounds such as benzene and phenol compounds, and olefin compounds.

Examples of the phenolic compound include unsubstituted or substituted phenols. Herein, the substituted phenol refers to an alkylphenol having a linear or branched alkyl group or a cycloalkyl group as a substituent, and the linear or branched alkyl group is a straight chain group having 1 to 6 carbon atoms. chain or branched chain alkyl. Examples of the linear or branched alkyl group include methyl, ethyl, isopropyl, butyl and hexyl. Examples of the cycloalkyl group include cyclohexyl.

Specific examples of the phenolic compound include 2-methylphenol, 3-methylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 2-ethylphenol, 3-isopropylphenol phenylphenol, 2-butylphenol and 2-cyclohexylphenol. In particular, phenol is preferred.

Examples of the olefin compound include compounds having a substituted or unsubstituted hydrocarbon group or hydrogen bonded to a carbon atom constituting the olefin double bond.

Examples of the substituent of the hydrocarbon group include a hydroxyl group, a halogen atom, a carbonyl group, an alkoxycarbonyl group, a cyano group and a nitro group. Examples of the hydrocarbon group include saturated hydrocarbon groups. Examples of the saturated hydrocarbon group include an alkyl group.

Specific examples of the olefin compound include olefins having 2 to 10 carbon atoms and cycloolefins having 4 to 10 carbon atoms.

Examples of the olefin having 2 to 10 carbon atoms include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, 2-butene, isobutylene, 2-pentene , 3-pentene, 2-hexene, 3-hexene, 4-methyl-1-pentene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene , 3-nonene, 2-decene and 3-decene.

Examples of the cycloolefin having 4 to 10 carbon atoms include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene and cyclodecane.

In the present invention, the organic compound is preferably an olefin compound, more preferably an olefin having 2-10 carbon atoms, even more preferably an olefin having 2-5 carbon atoms, particularly preferably propylene.

In the present invention, the organic compound can be used in any selected amount according to its kind, reaction conditions, etc., and is preferably used in an amount of 0.01 parts by weight or more relative to 100 parts by weight of the total amount of solvent in the liquid phase, more preferably in an amount of It is used in an amount of 0.1 part by weight or more. The upper limit of the organic compound is preferably 1000 parts by weight, more preferably 100 parts by weight, relative to 100 parts by weight of the total amount of the solvent in the liquid phase.

In the preparation method of the present invention, the titanosilicate (I) or its silylated form can be used in an appropriate amount according to the type of reaction, and the lower limit of the amount used is usually relative to the total amount of the solvent in the liquid phase It is 0.01wt%, preferably 0.1wt%, more preferably 0.5wt%, and its upper limit is 20wt%, preferably 10wt%, more preferably 8wt% relative to the total amount of solvent in the liquid phase.

Examples of the oxidation reaction in the present invention include epoxidation reaction of the olefin compound and hydroxylation reaction of the aromatic compound such as benzene or phenol compound.

Examples of the epoxidation reaction include a reaction by which the olefin compound is converted into a corresponding epoxy compound.

Examples of the hydroxylation reaction include a reaction of converting an aromatic compound into a phenol or a polyphenol compound by hydroxylating an aromatic ring of the aromatic compound.

The preparation method of the present invention is suitable for the epoxidation reaction of olefins with 2-10 carbon atoms, preferably olefins with 2-5 carbon atoms, especially propylene, using hydrogen peroxide as an oxidant.

In the preparation method of the present invention, the oxidized compound refers to an oxygen-containing compound obtained through the oxidation reaction. Examples of the oxidized compound include epoxy compounds obtained by the epoxidation reaction and phenol or polyphenol compounds obtained by the hydroxylation reaction.

In the preparation method of the present invention, the titanosilicate (I) may also be first contacted with hydrogen peroxide, and then reacted.

The hydrogen peroxide in the contacting may be used in the form of a hydrogen peroxide solution. The hydrogen peroxide concentration of the hydrogen peroxide solution is usually 0.0001wt%-50wt%. The hydrogen peroxide solution may be an aqueous solution or a solution obtained using a solvent other than water. The solvent other than water can be appropriately selected from, for example, solvents used in the oxidation reaction as an appropriate one. The contacting is usually carried out at a temperature ranging from 0°C to 100°C, more preferably from 0°C to 60°C.

In the production method of the present invention, when the oxidizing agent is hydrogen peroxide, hydrogen peroxide generated in the same reaction system as that of the oxidation reaction may be supplied to the reaction.

In the case where hydrogen peroxide is produced from the same reaction system as that of the oxidation reaction, the hydrogen peroxide can be produced, for example, from oxygen and hydrogen in the presence of a noble metal catalyst.

Examples of the noble metal catalyst include noble metals such as palladium, platinum, ruthenium, rhodium, iridium, osmium and gold, and alloys or mixtures thereof. Preferable examples of the noble metal include palladium, platinum and gold. The noble metal is more preferably palladium. For example, colloidal palladium can be used as the palladium (see, for example, Example 1 in Japanese Patent Laid-Open No. 2002-294301). The noble metal catalyst used may be a noble metal compound that is converted into a noble metal by reduction in the oxidation reaction system. The noble metal catalyst is preferably a palladium compound.

When palladium is used as the noble metal catalyst, metals other than palladium such as platinum, gold, rhodium, iridium, and osmium may also be added thereto and used in a mixture. Preferable examples of metals other than palladium include platinum.

Examples of the palladium compound include tetravalent and divalent palladium compounds.

Examples of tetravalent palladium compounds include sodium hexachloropalladate (IV) and potassium hexachloropalladate (IV). Examples of divalent palladium compounds include palladium(II) chloride, palladium(II) bromide, palladium(II) acetate, palladium(II) acetylacetonate, bis(benzonitrile)palladium(II) dichloride, bis(acetonitrile) ) dichloropalladium(II), bis(diphenylphosphino)ethanedichloropalladium(II), bis(triphenylphosphine)dichloropalladium(II), tetraamminepalladium(II) chloride ), palladium(II) tetraammine bromide, (1,5-cyclooctadiene)palladium(II) dichloride and palladium(II) trifluoroacetate.

The noble metal is usually supported on a carrier for use. The noble metals can be supported on titanosilicate (I) or oxides (such as silica, alumina, titania, zirconia and niobia), hydrates (such as niobic acid, zirconic acid, tungstic acid and titanic acid), carbon and mixtures thereof. When the noble metal is supported on a carrier other than titanosilicate (I), the carrier containing the noble metal supported thereon is mixed with the titanosilicate (I), and the mixture can be used as a catalyst. Among the supports other than titanosilicate (I), preferred examples thereof include carbon. Known carbon supports are activated carbon, carbon black, graphite, carbon nanotubes, and the like.

The noble metal-supported catalyst is prepared by a known method, for example, by supporting a noble metal compound on a carrier, followed by reduction. The noble metal compound can be supported by a conventional method known in the art such as impregnation.

The reduction method may be reduction using a reducing agent such as hydrogen or reduction using ammonia gas generated during thermal decomposition under an inert gas atmosphere. The reduction temperature varies depending on the type of noble metal compound and the like, but for tetraamminepalladium(II) chloride used as a noble metal compound, it is usually 100°C to 500°C, preferably 200°C to 350°C.

The noble metal-supported catalyst generally contains noble metal in the range of 0.01-20 wt%, preferably 0.1-5 wt%.

The lower limit of the noble metal used is usually 0.001 parts by weight, preferably 0.01 parts by weight, more preferably 0.1 parts by weight relative to 100 parts of titanosilicate (I). The upper limit of the noble metal used is usually 100 parts by weight, preferably 20 parts by weight, more preferably 5 parts by weight, relative to 100 parts by weight of titanosilicate (I).

In the present invention, conditions including reaction temperature and reaction pressure can be set arbitrarily according to the kind, amount, etc. of the materials used.

The lower limit of the reaction temperature is preferably 0°C, more preferably 40°C, and the upper limit is preferably 200°C, more preferably 150°C.

The lower limit of the reaction pressure is preferably 0.1 MPa, more preferably 1 MPa, and the upper limit is preferably 20 MPa, more preferably 10 MPa.

The reaction product can be collected by methods well known in the art such as separation by distillation.

Hereinafter, the production method of the present invention will be described in detail by taking an example of a method for producing an epoxy compound by oxidation (epoxidation) of an olefin compound.

In this production method, the reaction is usually carried out in a liquid phase containing a solvent. Examples of the solvent include water, an organic solvent, and a mixture of water and the organic solvent.

Examples of the organic solvent include alcohols, ketones, nitriles, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, esters, and mixtures thereof.

Examples of the aliphatic hydrocarbons include aliphatic hydrocarbons having 5 to 10 carbon atoms, such as hexane and heptane. Examples of the aromatic hydrocarbons include aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene, toluene, and xylene.

Examples of the alcohol include monohydric alcohols having 1 to 6 carbon atoms and dihydric alcohols having 2 to 8 carbon atoms. The alcohol is preferably an aliphatic alcohol having 1-8 carbon atoms, more preferably a monohydric alcohol having 1-4 carbon atoms, such as methanol, ethanol, isopropanol and tert-butanol, even more preferably tert-butanol.

The nitriles are preferably C ₂ -C ₄ alkylnitriles (such as acetonitrile, propionitrile, isobutyronitrile and butyronitrile) and benzonitrile, most preferably acetonitrile.

In view of catalyst activity and selectivity, the organic solvent is preferably alcohol or nitrile.

In the method for preparing epoxy compounds, the presence of a buffer in the reaction system can prevent the catalyst activity from being reduced, further improve the catalyst activity, or improve the use efficiency of the gas source.

The buffer is usually present in the reaction system in a form in which it is dissolved in the liquid phase. When hydrogen peroxide produced in the same reaction system as that of the epoxidation is used as an oxidizing agent, the buffer may be previously contained in a part of the noble metal complex. In one approach, for example, ammonium complexes such as tetraamminepalladium(II) chloride are loaded onto the support by impregnation and then reduced to form residual ammonium ions, allowing the buffer to form in the epoxidation reaction. . The buffer is usually added in an amount of 0.001 mmol/kg-100 mmol/kg per 1 kg of solvent in the liquid phase.

Examples of the buffer include buffers comprising the following 1) and 2): 1) selected from sulfate ions, hydrogen sulfate ions, carbonate ions, bicarbonate ions, phosphate ions, hydrogen phosphate ions, phosphoric acid Dihydrogen ion, hydrogen pyrophosphate ion, pyrophosphate ion, halide ion, nitrate ion, hydroxide ion and C ₁ -C ₁₀ carboxylate ion anion, and 2) selected from ammonium, C ₁ - _C20 alkyl ammonium, _C7 - _C20 alkyl aryl ammonium, cations in alkali metals and alkaline earth metals.

Examples of the C ₁ -C ₁₀ carboxylate ion include acetic acid, formic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, octanoic acid, capric acid and benzoate ion.

Examples of the alkylammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetra-n-propylammonium ion, tetra-n-butylammonium ion and cetyltrimethylammonium ion root ion. Examples of the alkali metal and alkaline earth metal cations include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium cations.

Preferred examples of the buffer include: ammonium salts of inorganic acids such as ammonium sulfate, ammonium hydrogensulfate, ammonium carbonate, ammonium hydrogencarbonate, diammonium hydrogenphosphate, ammonium dihydrogenphosphate, ammonium phosphate, ammonium hydrogenpyrophosphate, pyrophosphoric acid ammonium, ammonium chloride and ammonium nitrate; and ammonium salts of C ₁ -C ₁₀ carboxylic acids such as ammonium acetate. Preferable examples of the ammonium salt include ammonium dihydrogenphosphate.

In the method for preparing epoxy compounds, when the hydrogen peroxide used is synthesized from oxygen and hydrogen in the same reaction system as that of the oxidation reaction, the presence of the quinoid compound in the reaction system can further Improves selectivity for oxidized compounds.

Examples of the quinone compound include p-quinone compounds and phenanthrene quinone compounds represented by the following formula (1):

Wherein, R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, or R ¹ and R ² are bonded to each other at their ends and together with the carbon atom to which they are bonded represent a naphthalene ring that may be substituted, or R ³ and R ⁴ are bonded to each other at their terminals and together with the carbon atom to which they are bonded represent a naphthalene ring which may be substituted, and X and Y are the same or different from each other and represent an oxygen atom or an NH group.

Examples of compounds of formula (1) include:

1) A quinone compound (1A) represented by formula (1), wherein R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms, and both X and Y are oxygen atoms;

2) A quinoneimine compound (1B) represented by formula (1), wherein R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms, and X and Y are oxygen atoms and NH groups, respectively; and

3) A quinonediimine compound (1C) represented by formula (1), wherein R ¹ , R ² , R ³ and R ⁴ represent hydrogen atoms, and X and Y are NH groups.

The quinone compounds represented by formula (1) include the following anthraquinone compounds (2):

wherein X and Y are as defined in formula (1); R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different from each other and represent a hydrogen atom, hydroxyl or alkyl (eg C ₁ -C ₆ alkyl, such as methyl , ethyl, propyl, butyl and pentyl).

In formulas (1) and (2), X and Y preferably represent an oxygen atom.

Dihydro forms of partially hydrogenated quinoids may be formed under certain reaction conditions. These dihydro forms are useful in epoxidations.

Examples of the quinone type compound include benzoquinone, naphthoquinone, anthraquinone, alkylanthraquinone compound, polyhydroxyanthraquinone, p-quinone type compound and o-quinone type compound.

Examples of the alkylanthraquinone compound include: 2-alkylanthraquinone compounds such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, 2-methylanthraquinone, 2 -Butylanthraquinone, 2-tert-amylanthraquinone, 2-isopropylanthraquinone, 2-sec-butylanthraquinone and 2-sec-amylanthraquinone; and polyalkylanthraquinone compounds such as 1,3 - diethylanthraquinone, 2,3-dimethylanthraquinone, 1,4-dimethylanthraquinone and 2,7-dimethylanthraquinone. Examples of polyhydroxyanthraquinones include 2,6-dihydroxyanthraquinones. Examples of the p-quinone type compound include naphthoquinone and 1,4-phenanthrenequinone. Examples of o-quinone type compounds include 1,2-, 3,4-, and 9,10-phenanthrenequinone.

Preferred examples of the quinoid compound include: anthraquinone; and 2-alkylanthraquinone compounds shown in formula (2), wherein X and Y are oxygen atoms, R is a ² -substituted alkyl group, and R ^is , R ⁷ and R ⁸ represent a hydrogen atom.

The amount of the quinoid compound used is generally 0.001 mmol/kg-500 mmol/kg per 1 kg of solvent in the liquid phase.

The amount of the quinoid compound is preferably 0.01 mmol/kg-50 mmol/kg.

In the method of the present invention, an ammonium salt, an alkylammonium salt or an alkylarylammonium salt may also be added to the reaction system simultaneously with the quinoid compound.

The quinoid compound can also be produced by oxidizing the dihydro form of the quinoid compound in the reaction system with oxygen or the like. For example, a hydroquinone compound such as hydroquinone or 9,10-anthracenol is added to the liquid phase and oxidized with oxygen in the reaction system to form a quinone compound that can be used subsequently.

Examples of the dihydro form of the quinoid compound include compounds represented by the following formulas (3) and (4), which are dihydro forms of compounds of the formulas (1) and (2):

wherein R ¹ , R ² , R ³ , R ⁴ , X and Y are all as defined in formula (1), and

Wherein X, Y, R ⁵ , R ⁶ , R ⁷ and R ⁸ are all as defined in formula (2).

In said formulas (3) and (4), X and Y preferably represent an oxygen atom.

Preferable examples of the dihydro forms of the quinoid compounds include dihydro forms corresponding to the preferred quinoid compounds.

Examples of the reaction method used in the method for producing the epoxy compound include fixed-bed flow reaction of slurry and total mixed flow reaction.

The olefinic compound may be epoxidized by oxidizing the olefinic compound with a pre-made peroxide in any reactive gas atmosphere without limitation.

When the peroxide is prepared from oxygen and hydrogen in the same reaction system as that of the oxidation reaction in the presence of a noble metal, oxygen and hydrogen are usually supplied to the reaction at a partial pressure ratio of 1:50-50:1 device. The partial pressure ratio of oxygen and hydrogen is preferably oxygen:hydrogen=1:2-10:1. In the case of too high a partial pressure ratio of oxygen to hydrogen (oxygen/hydrogen), the epoxide yield may decrease. In contrast, at too low a partial pressure ratio of oxygen to hydrogen (oxygen/hydrogen), epoxide selectivity may decrease due to an increase in alkane compound by-products.

In the reaction of the present invention, the oxygen and hydrogen gases may be diluted. Examples of the gas used in the dilution include nitrogen, argon, carbon dioxide, methane, ethane and propane. The gas used for the dilution is used in any concentration without limitation.

Examples of oxygen as a raw material include oxygen and air. The oxygen used may be oxygen produced by an inexpensive pressure swing method, or high-purity oxygen produced by cryogenic separation or the like, if necessary.

As far as the lower limit is concerned, the epoxidation of the present invention is generally carried out at a reaction temperature of 0°C, preferably 40°C, more preferably 50°C, and as regards the upper limit, at 200°C, preferably 150°C, more preferably 120°C for the reaction temperature.

At too low a reaction temperature, the reaction rate decreases. In comparison, at too high a reaction temperature, by-products increase due to side reactions.

The reaction is carried out under any pressure without particular limitation, and is usually carried out at 0.1 MPa to 20 MPa, more preferably 1 MPa to 10 MPa in gauge pressure. The reaction product can be collected by methods well known in the art such as separation by distillation.

In the epoxidation of the present invention, the titanosilicate (I) or its silylated form can be used in an appropriate amount according to the type of reaction, and the lower limit of the amount relative to the total amount of solvent in the liquid phase is usually 0.01wt%, preferably 0.1wt%, more preferably 0.5wt%, and its upper limit relative to the total amount of solvent in the liquid phase is 20wt%, preferably 10wt%, more preferably 8wt%.

In the epoxidation of the present invention, the olefin compound can be used in an appropriate amount according to its type, reaction conditions, etc., and the lower limit of its amount is preferably 0.01 parts by weight, 100 parts by weight of the total amount of solvent in the liquid phase, More preferably 0.1 parts by weight, more preferably 1 part by weight, and the upper limit of the amount used is preferably 1000 parts by weight, more preferably 100 parts by weight, and even more preferably 50 parts by weight relative to 100 parts by weight of the total amount of solvent in the liquid phase .

In the epoxidation of the present invention, the oxidizing agent can be used in an arbitrary amount selected according to the kind of the olefin compound, reaction conditions, etc., and is preferably used in an amount of 0.1 parts by weight or more with respect to 100 parts by weight of the olefin compound used, more preferably in an amount of 1 part by weight or more. The upper limit of the oxidizing agent used is preferably 100 parts by weight, more preferably 50 parts by weight, relative to 100 parts by weight of the olefin compound.

Hereinafter, the present invention will be described with reference to examples.

In the examples of the specification of the present invention, various measurements were performed according to the following methods.

1. Ti (titanium), Si (silicon) and B (boron) content

These contents were determined by alkali fusion, dissolution in nitric acid and using SUMIGRAPH NCH-22F type (Sumika Chemical Analysis Service, Ltd.) to measure the ICP emission spectrum.

2. N (nitrogen) content

The N content was determined by oxygen cycle combustion and using SUMIGRAPH NCH-22F type (Sumika Chemical Analysis Service, Ltd.) TCD detection system to measure.

3. UV-visible absorption spectrum (UV-Vis spectrum)

The UV-Vis spectra were obtained using a diffuse reflectance accessory (HARRICK Scientific Products (Praying Mantis) UV-visible spectrophotometer (manufactured by JASCO Corp (V-7100)) was detected by the diffuse reflectance method.

Detection wavelength: 200-500nm

Baseline Standard: Spectralon

4. Specific surface area (SN ₂ ) determined by nitrogen adsorption

About 100 mg of sample was degassed at 150°C for 8 hours. The nitrogen adsorption isotherm was then measured at an absorption temperature of 77K at a constant volume using BELSORP-mini (manufactured by BEL JAPAN INC.), and the specific surface area was calculated by the multipoint BET method.

In this multi-point BET method, at least 3 points whose correlation coefficient is 0.999 or higher in a relative pressure range of 0 to 0.2 and exhibit as high a correlation as possible are used.

5. Specific surface area ( _SH2O ) determined by water vapor adsorption

A 100 mg sample was degassed at 150°C for 8 hours. The water vapor adsorption isotherm was then measured at an absorption temperature of 298K at a constant volume using BELSORP-aqua3 (manufactured by BEL JAPAN INC.), and the specific surface area was calculated by the multipoint BET method.

In this multi-point BET method, at least 3 points whose correlation coefficient is 0.999 or higher in a relative pressure range of 0 to 0.2 and exhibit as high a correlation as possible are used.

6. X-ray diffraction pattern

The X-ray diffractogram was measured using an X-ray diffractometer (trade name: RINT2500V, manufactured by Rigaku Corp.) with copper Kα X-ray radiation under the following conditions.

Output: 40kV-300mA

Scanning range: 2θ=5-30º

Scanning speed: 1º/min

Launch slit: 1º

Scattering slit: 1º

Receiving slit: 0.3mm

Sampling width: 0.02º

The interplanar distance d and the peak intensity were calculated using the X-ray diffraction analysis software JADE6 produced by MDI (Material Data Incorporated) under the following setting conditions.

Smooth: smooth score = 15

Background removal: peak width threshold: 0.100º, peak intensity threshold: 0.01 cps

Kα2 removal: intensity ratio (Kα2/Kα1) = 0.50

Peak Search: Peak Width Threshold: 0.500º, Peak Intensity Threshold = 500cps

7. Composition of reaction products

The composition was determined by gas chromatography (trade name: HP5890 series II, manufactured by Agilent Technologies).

Herein, the titanosilicates (I) obtained in the following preparation examples are referred to as catalysts A-M, respectively.

catalyst A preparation of

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402 g of pure water, 112 g of tetra-n-butyl orthotitanate [TBOT] (produced by Wako Pure Chemical Industries, Ltd.), 565 g of boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D, manufactured by Cabot Corp.) were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 96 hours for hydrothermal synthesis to obtain a suspension solution.

After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 10. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 522 g of Layered Compound 1 .

To 75 g of the layered compound 1 was added 3750 mL of 2M nitric acid, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was then vacuum dried at 150° C. until no weight loss was seen to obtain 60 g of a white powder (solid product 1 ). The result of examining the X-ray diffraction pattern confirmed that the solid product 1 had a MWW precursor structure. The solid product 1 contained 1.67% by mass of Ti and had a Si/N ratio of 105. The result of detecting UV-visible absorption spectrum proves that the solid product 1 is titanosilicate. The SH ₂ O/SN ₂ ratio of the solid product 1 was 0.58.

20 g of the solid product 1 were calcined at 530 °C for 6 hours to obtain 18 g of Ti-MWW (solid product 2). X-ray diffraction pattern examination proves that the obtained powder has MWW structure. The solid product 2 contained 1.89% by mass of Ti and had a Si/N ratio of 2005. The result of detecting the UV-visible absorption spectrum proves that the solid product 2 is titanosilicate. The SH ₂ O/SN ₂ ratio of the solid product 1 was 0.38.

At 25°C, 200 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 400 g of pure water, and 135 g of the solid product 2 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 134 g of a white powder (catalyst A).

As a result of examining the X-ray diffraction pattern, it was confirmed that the catalyst A had a MWW precursor structure. The catalyst A contained 1.76% by mass of Ti and had a Si/N ratio of 11. The result of detecting the UV-visible absorption spectrum proves that the catalyst A is titanosilicate. The SH ₂ O/SN ₂ ratio of the catalyst A is 0.99.

20 g of the catalyst A were calcined at 530 °C for 6 hours to obtain 18 g of Ti-MWW powder (solid product 3). X-ray diffraction pattern detection proves that the solid product 3 has a MWW structure. The solid product 3 contained 1.95% by mass of Ti and had a Si/N ratio of 1003. The result of detecting UV-visible absorption spectrum proves that the solid product 3 is titanosilicate. The SH ₂ O/SN ₂ ratio of the solid product 3 was 0.41. On the other hand, 777 g of 2N nitric acid was added to 15 g of Catalyst A, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was vacuum dried at 150° C. until no weight loss was seen to obtain 12 g of white powder (solid product 4). The result of examining the X-ray diffraction pattern confirmed that the solid product 4 had a MWW precursor structure. The solid product 4 contained 1.42% by mass of Ti and had a Si/N ratio of 79. The result of detecting the UV-visible absorption spectrum proves that the solid product 4 is titanosilicate. The SH ₂ O/SN ₂ ratio of the solid product 4 was 0.52.

catalyst B preparation of

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402 g of pure water, 565 g of boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D, produced by Cabot Corp.) were dissolved in an autoclave and then aged for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours to obtain a suspension solution. After filtering the suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 10. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 495 g of white powder b1. As a result of examining the X-ray diffraction pattern, it was confirmed that the white powder b1 had a layered structure. The white powder b1 contained 1.5 wt% boron and had a silicon content of 34.8%.

To 75 g of the layered borosilicate thus obtained (white powder b1) were added 3885 g of 2N nitric acid and 9.5 g of tetra-n-butyl orthotitanate [TBOT] (provided by Wako Pure Chemical Industries, Ltd.), and reflux the mixture for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid matter was then vacuum dried at 150° C. until no weight loss was seen to obtain 60 g of white powder b2. As a result of examining the X-ray diffraction pattern, it was confirmed that the white powder b2 has a MWW precursor structure. The white powder b2 contained 1.39% by mass of Ti, and had a Si/N ratio of 56. The result of detecting the UV-visible absorption spectrum proves that the white powder b2 is titanosilicate.

30 g of the white powder b2 was calcined at 530° C. for 6 hours to obtain 27 g of powder b3. The detection of X-ray diffraction pattern proves that the obtained powder b3 has a MWW structure. In addition, the powder b3 contained 1.42wt% Ti by ICP emission spectroscopic analysis.

40 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 27 g of powder b3 were dissolved in an autoclave under an air atmosphere at 25° C., followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 26 g of white powder b4 (catalyst B). As a result of examining the X-ray diffraction pattern, it was confirmed that the white powder b4 had a MWW precursor structure. The catalyst B contained 1.40% by mass of Ti and had a Si/N ratio of 10. The result of detecting the UV-visible absorption spectrum proves that the catalyst B is titanosilicate. The SH ₂ O/SN ₂ ratio of the catalyst B is 1.28.

catalyst C preparation of

40 g of hexamethyleneimine (manufactured by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 27 g of the solid product 2 were dissolved in an autoclave at 25° C. in an air atmosphere, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 26 g of a white powder (catalyst C). The result of examining the X-ray diffraction pattern confirmed that the catalyst C had a MWW precursor structure. The catalyst C contained 1.70% by mass of Ti and had a Si/N ratio of 12. The result of detecting the UV-visible absorption spectrum proves that the catalyst C is titanosilicate. The SH ₂ O/SN ₂ ratio of the catalyst C is 0.76.

catalyst D. preparation of

At 25°C, 40 g of piperidine (manufactured by Wako Pure Chemical Industries, Ltd.), 80 g of pure water and 15 g of the solid product 1 were dissolved in an autoclave under an air atmosphere, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 11 g of a white powder (catalyst D). As a result of examining the X-ray diffraction pattern, it was confirmed that the white powder had a MWW precursor structure. The catalyst D contained 1.78% by mass of Ti and had a Si/N ratio of 11. The result of detecting the UV-visible absorption spectrum proves that the catalyst D is titanosilicate. The SH ₂ O/SN ₂ ratio of the catalyst D is 0.96.

catalyst E. preparation of

At 25°C, 60 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.) and 5 g of the solid product 1 were mixed in a glass beaker and allowed to stand at 25° C. for 24 hours. Next, after filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. The solid matter was further vacuum dried at 150° C. until no weight loss was seen to obtain 4.9 g of white powder e (Catalyst E). The results of detecting X-ray diffraction pattern and UV-visible absorption spectrum confirmed that the white powder e had a Ti-MWW precursor structure. The catalyst E contained 1.83% by mass of Ti and had a Si/N ratio of 16.

catalyst f preparation of

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402 g of pure water, 112 g of tetra-n-butyl orthotitanate [TBOT] (produced by Wako Pure Chemical Industries, Ltd.), 565 g of boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D, manufactured by Cabot Corp.) were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 96 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.7. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 547 g of a layered compound.

To 75 g of the layered compound was added 3750 mL of 2M nitric acid, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid matter was then vacuum-dried at 150° C. for 4 hours to obtain 60 g of white powder f1. The results of examining the X-ray diffraction pattern and the UV-visible absorption spectrum confirmed that the white powder f1 was a Ti-MWW precursor. As a result of elemental analysis, the white powder f1 contained 1.60 wt % of Ti (titanium), and the Si/N ratio was 105.

20 g of said white powder f1 were calcined at 530°C for 6 hours to obtain 18 g of Ti-MWW (powder f2). The results of X-ray diffraction pattern detection and UV-visible absorption spectrum prove that the powder f2 is Ti-MWW.

At 25°C, 20 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 20 g of hexamethyleneimine (produced by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 10 g of powder f2 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 10 g of white powder f3 (catalyst F). As a result of examining the X-ray diffraction pattern and UV-visible absorption spectrum, it was confirmed that this white powder f3 was titanosilicate. The white powder f3 has a Ti-MWW precursor structure. The catalyst F contained 1.65% by mass of Ti and had a Si/N ratio of 11.

catalyst G preparation of

Catalyst G is based on Chemical Communication 1026-1027, (2002) were prepared as follows.

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402 g of pure water, 565 g of boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D, produced by Cabot Corp.) were dissolved in an autoclave and then aged for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.6. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 495 g of a solid product g1 (layered borosilicate). The content of B in the solid product g1 was 1.50% by mass, and the content of Si was 34.8% by mass.

To 75 g of the solid product g1 was added 3750 mL of 2M nitric acid, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was vacuum dried at 150°C until no weight loss was seen to obtain 57 g of white powder g2. As a result of examining the X-ray diffraction pattern, it was confirmed that the white powder g2 had a MWW precursor structure. 40 g of said white powder g2 was calcined at 530° C. for 6 hours to obtain 36 g of solid powder g3 (B-MWW). X-ray diffraction pattern detection proves that the solid product g3 has a MWW structure.

At 25°C, 29 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 118 g of pure water, 5.3 g of TBOT (produced by Wako Pure Chemical Industries, Ltd.) and 20 g of B-MWW were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.3. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 23 g of solid product g4.

To 15 g of the solid product g4 was added 750 mL of 2M nitric acid, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was then vacuum dried at 150° C. until no further weight loss was seen to obtain 12 g of white powder g5. The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder g5 has a Ti-MWW precursor structure. The white powder g5 contained 1.94% by mass of Ti, and had a Si/N ratio of 102.

10 g of the white powder g5 was calcined at 530° C. for 6 hours to obtain 9 g of solid product 6 (Ti-MWW). The results of X-ray diffraction pattern detection prove that the solid product g6 has a MWW structure.

At 25°C, 40 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 7 g of solid product g6 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 6 g of white powder g7 (catalyst G).

The results of examining the X-ray diffraction pattern and UV-visible absorption spectrum confirmed that the white powder g7 was titanosilicate having a Ti-MWW precursor structure. The catalyst G contained 1.96% by mass of Ti and had a Si/N ratio of 13.

catalyst h preparation of

At 25 °C, 257 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 686g pure water, 6.4g TBOT (produced by Wako Pure Chemical Industries, Ltd.), 162g boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 117 g of fumed silica (trade name: Cab-O-Sil M7D, manufactured by Cabot Corp.) were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.2. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 125 g of solid product h1.

To 75 g of the solid product h1 were added 3750 mL of 2M nitric acid and 9.5 g of TBOT, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was vacuum dried at 150° C. until no weight loss was seen to obtain 59 g of white powder h2. The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder h2 was a Ti-MWW precursor. The white powder h2 contained 1.67% by mass of Ti, and had a Si/N ratio of 46.

20 g of said white powder h2 were calcined at 530° C. for 6 hours to obtain 18 g of solid product h3 (Ti-MWW). The result of X-ray diffraction pattern detection proves that the solid product h3 has a MWW structure.

At 25°C, 40 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 10 g of solid product h3 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 11 g of white powder h4 (catalyst H). The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder h4 was a titanosilicate having a Ti-MWW precursor structure. The catalyst H contained 1.76% by mass of Ti and had a Si/N ratio of 10.

catalyst I preparation of

At 25 °C, 257 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 686 g of pure water, 13.2 g of TBOT (manufactured by Wako Pure Chemical Industries, Ltd.), 162 g of boric acid, and 117 g of fumed silica (trade name: Cab-O-Sil M7D) were dissolved under high pressure kettle, then aged for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.4. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 145 g of solid product il.

To 75 g of the solid product il was added 3750 mL of 2M nitric acid and 9.5 g of TBOT, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid material was vacuum dried at 150° C. until no weight loss was seen to obtain 49 g of white powder i2. The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder i2 has a Ti-MWW precursor structure. The white powder i2 contained 1.93% by mass of Ti, and had a Si/N ratio of 61.

30 g of the white powder i2 were calcined at 530° C. for 6 hours to obtain 27 g of solid product i3 (Ti-MWW). X-ray diffraction pattern detection proves that the solid product i3 has a MWW structure.

At 25°C, 40 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 80 g of pure water, and 20 g of solid product i3 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 19 g of white powder i4 (Catalyst I). The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the catalyst I was a titanosilicate having a Ti-MWW precursor structure. The catalyst I contained 2.03% by mass of Ti and had a Si/N ratio of 11.

catalyst J preparation of

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402g pure water, 22.4g TBOT (produced by Wako Pure Chemical Industries, Ltd.), 565g boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D) were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.4. Next, the solid matter was dried at 50°C until no weight loss was seen to obtain 564 g of a solid product j1.

To 75 g of the solid product j1 were added 3750 mL of 2M nitric acid and 9.5 g of TBOT, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid matter was further vacuum dried at 150° C. until no weight loss was seen to obtain 62 g of white powder j2. The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder j2 was a Ti-MWW precursor. The white powder j2 contained 1.56% by mass of Ti, and had a Si/N ratio of 55.

60 g of said white powder j2 was calcined at 530° C. for 6 hours to obtain 54 g of solid product j3 (Ti-MWW). X-ray diffraction pattern detection proves that the solid product j3 has a MWW structure. The above steps were carried out 2 more times to obtain a total of 162 g of the solid product j3.

At 25°C, 300 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 600 g of pure water and 110 g of the solid product j3 were dissolved in an autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 24 hours to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was about 9. Next, the solid matter was vacuum-dried at 150° C. until no weight loss was seen to obtain 108 g of white powder j4 (catalyst J). The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder j4 was titanosilicate having a Ti-MWW precursor structure. The catalyst J contained 1.58% by mass of Ti and had a Si/N ratio of 10.

catalyst K preparation of

The catalyst J was silylated based on the method described in Japanese Patent Laid-Open No. 2003-326171. Specifically, 11 g of 1,1,1,3,3,3-hexamethyldisilazane (provided by Wako Pure Chemical Industries, Ltd.), 175 mL of toluene (produced by Wako Pure Chemical Industries, Ltd.), and 15 g of the catalyst J, and refluxed the mixture for 3 hours for silylation. After filtering the resulting reaction mixture, the resulting solid matter was washed in this order with a mixed solvent of 500 mL of acetone and 1 L of water/acetonitrile (=1/4, weight ratio), and then vacuum-dried at 150 °C until no weight loss was seen to obtain 14 g of white powder (catalyst K). The catalyst K contained 1.61% by mass of Ti and had a Si/N ratio of 13.

catalyst L preparation of

At 25 °C, 899 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 2402 g of pure water, 112 g of tetra-n-butyl orthotitanate [TBOT] (produced by Mitsubishi Gas Chemical Co., Inc.), 565 g of boric acid (produced by Wako Pure Chemical Industries, Ltd.) and 410 g of fumed silica (trade name: Cab-O-Sil M7D, manufactured by Cabot Corp.) was dissolved in the autoclave, followed by aging for 1.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 8 hours, and then kept at 160° C. for 120 hours for hydrothermal synthesis to obtain a suspension solution. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 10.8. Next, the solid matter was dried at 50° C. until no weight loss was seen to obtain 518 g of a layered compound.

To 75 g of the layered compound was added 3750 mL of 2M nitric acid, and the mixture was refluxed for 20 hours. After filtering the obtained reaction mixture, the obtained solid matter was washed with water until the pH of the washing liquid was about neutral. The solid matter was then vacuum-dried at 150° C. for 4 hours to obtain 60 g of white powder n1. The results of examining the X-ray diffraction pattern and the UV-visible absorption spectrum confirmed that the white powder n1 was a Ti-MWW precursor. As a result of elemental analysis, the white powder n1 contained 1.60 wt % of Ti (titanium), and had a Si/N ratio of 90.

20 g of said white powder n1 were calcined at 530°C for 6 hours to obtain 18 g of Ti-MWW (powder n2). The results of X-ray diffraction pattern detection and UV-visible absorption spectrum prove that the powder n2 is Ti-MWW.

At 25°C, 45 g of piperidine (provided by Wako Pure Chemical Industries, Ltd.), 90 g of pure water, and 15 g of powder n2 were dissolved in an autoclave, followed by aging for 0.5 hours. Further, the autoclave was sealed, and the obtained gel was heated under stirring for 4 hours, and then kept at 160° C. for 16 hours to obtain a suspension solution. After filtering the obtained suspension solution, the solid matter was vacuum-dried at 50° C. until no weight loss was seen to obtain 5 g of white powder n3 (catalyst L). The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder n3 was a titanosilicate having a Ti-MWW precursor structure. The catalyst L contained 1.37% by mass of Ti, and had a Si/N ratio of 8.7.

catalyst m preparation of

At 25°C, 5 g of the catalyst A, 90 g of pure water and 10 g of acetic acid (by Wako Pure Chemical Industries, Ltd.) was added to a three-necked glass flask, and the mixture was stirred in air at 75°C for 6 hours. After filtering the obtained suspension solution, the obtained solid matter was washed with water until the pH of the washing liquid was 6.7. Next, the solid matter was dried at 150° C. until no weight loss was seen to obtain 3.9 g of white powder m1 (catalyst M). The results of detecting the X-ray diffraction pattern and the UV-visible absorption spectrum pattern confirmed that the white powder m1 was a titanosilicate having a Ti-MWW precursor structure. The catalyst M contained 1.82% by mass of Ti and had a Si/N ratio of 31.

Pd/ Activated carbon ( AC )catalyst

The Pd/activated carbon (AC) catalyst was prepared by the method described below. To a 1-L eggplant-shaped flask was added 3 g of activated carbon (provided by Wako Pure Chemical) washed with 2 L of water in advance Industries, Ltd.), add 300ml of water, and stir the mixture in air at 25°C. To this suspension, 40 ml of an aqueous solution containing 0.3 mmol of palladium tetraammine chloride prepared separately was slowly added dropwise in air at 25°C. After the dropwise addition was complete, the suspension was further stirred at 25° C. in air for 6 hours. After the stirring was completed, the moisture was removed by a rotary evaporator, and the residue was vacuum-dried at 80° C. for 6 hours, and further calcined at 300° C. in a nitrogen atmosphere for 6 hours to obtain a Pd/AC catalyst.

Tables 1-4 show the X-ray diffraction pattern data for catalysts A-M, solid products 1-5, powders b3 and f2, solid products g6, h3 and i3, and powder n2.

Table 1. Interplanar distance d[Å]

In the respective tables, X ¹ /X ² represents the ratio of the peak intensity X ¹ at the interplanar distance 9.0±0.3 Å to the peak intensity X ² at the interplanar distance 3.4±0.1 Å.

Table 2. Interplanar distance d[Å]

Table 3. Interplanar distance d[Å]

Table 4. Interplanar distance d[Å]

When used in Examples 1-4 and Comparative Examples 1-4 described below, all catalysts were contacted with hydrogen peroxide prior to reaction as described below. The catalyst was placed in a water/acetonitrile (1/4 (weight ratio)) solution containing 0.1 wt% hydrogen peroxide at a ratio of 100 g of the solution to 0.05 g of the catalyst for 1 hour at a temperature of 25°C. After filtering the solution containing the catalyst, the collected catalyst was washed with 500 mL of water. The catalyst thus washed was further vacuum-dried at 150° C. for 1 hour, and then used for the reaction.

Example 1

A solution of 0.2 wt% H ₂ O ₂ , 19.96 wt% water, and 79.84 wt% acetonitrile was prepared using 30% H ₂ O ₂ aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), acetonitrile, and ion-exchanged water. 60 g of the prepared solution and 0.010 g of the catalyst A previously treated with hydrogen peroxide were placed in a 100 mL stainless steel autoclave. Next, the autoclave was transferred to an ice bath, and 1.2 g of liquid propylene was charged thereinto. The pressure of the reaction system was further increased to 2 MPa-G using argon. The autoclave was placed in a hot water bath at 60°C and removed from the hot water bath after 1 hour. Samples were taken and analyzed using gas chromatography. As a result, 3.86 mmol of propylene oxide was produced.

Example 2

Propylene oxide was prepared in the same steps as in Example 1 except that the catalyst B was used instead of the catalyst A. As a result, 3.40 mmol of propylene oxide was produced.

Example 3

Propylene oxide was prepared in the same steps as in Example 1 except that the catalyst D was used instead of the catalyst A. As a result, 3.73 mmol of propylene oxide was produced.

Example 4

Propylene oxide was prepared in the same steps as in Example 1 except that the catalyst E was used instead of the catalyst A. As a result, 3.73 mmol of propylene oxide was produced.

Comparative Example 1

Propylene oxide was prepared in the same steps as in Example 1 except that the solid product 1 was used instead of the catalyst A. As a result, 3.21 mmol of propylene oxide was produced.

Comparative Example 2

Propylene oxide was prepared in the same steps as in Example 1 except that the solid product 2 was used instead of the catalyst A. As a result, 2.59 mmol of propylene oxide was produced.

Comparative Example 3

Propylene oxide was prepared in the same steps as in Example 1 except that the solid product 3 was used instead of the catalyst A. As a result, 3.18 mmol of propylene oxide was produced.

Comparative Example 4

Propylene oxide was prepared in the same steps as in Example 1 except that the solid product 4 was used instead of the catalyst A. As a result, 2.71 mmol of propylene oxide was produced.

Example 5

A continuous reaction was carried out under the conditions of temperature 60°C, pressure 4 MPa (gauge pressure), and residence time 15 minutes, wherein 1.98 g of the catalyst A was placed in a 0.5 L autoclave and fed therein at a rate of 500 mL/min. Nitrogen, propylene was supplied at a rate of 92 g/Hr and a solution of 7 wt% _H2O2 in water/ _acetonitrile (weight ratio, water/acetonitrile = 20/80) was supplied at a rate of 652 mL/Hr, while the reaction mixture was passed through a filter from the out of the autoclave.

The liquid and gas phases taken out after 9 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 730 mmol/Hr, propylene glycol was produced at a yield of 6.87 mmol/Hr, and the conversion rate of hydrogen peroxide was 98.2%.

Example 6

Propylene oxide was prepared in the same steps as in Example 5 except that the catalyst B was used instead of the catalyst A. The liquid and gas phases taken out after 32 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 737mmol/Hr, propylene glycol was produced at a yield of 7.44mmol/Hr, and the conversion rate of hydrogen peroxide was 98.5%.

Example 7

Propylene oxide was prepared in the same steps as in Example 5 except that the catalyst C was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 715 mmol/Hr, propylene glycol was produced at a yield of 3.25 mmol/Hr, and the conversion rate of hydrogen peroxide was 93.7%.

Example 8

Propylene oxide was prepared in the same steps as in Example 5, except that the catalyst D was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 744 mmol/Hr, propylene glycol was produced at a yield of 11.10 mmol/Hr, and the conversion rate of hydrogen peroxide was 98.1%.

Example 9

Propylene oxide was prepared in the same steps as in Example 5 except that the catalyst E was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 677 mmol/Hr, propylene glycol was produced at a yield of 5.53 mmol/Hr, and the conversion rate of hydrogen peroxide was 89.9%.

Example 10

Propylene oxide was prepared in the same steps as in Example 5 except that the catalyst F was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 633 mmol/Hr, propylene glycol was produced at a yield of 2.36 mmol/Hr, and the conversion rate of hydrogen peroxide was 93.8%.

Example 11

Propylene oxide was prepared in the same steps as in Example 5 except that the catalyst G was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 665 mmol/Hr, propylene glycol was produced at a yield of 7.00 mmol/Hr, and the conversion rate of hydrogen peroxide was 98.8%.

Comparative Example 5

Propylene oxide was prepared in the same steps as in Example 5, except that the solid product 1 was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 606 mmol/Hr, propylene glycol was produced at a yield of 4.52 mmol/Hr, and the conversion rate of hydrogen peroxide was 79.5%.

Example 12

The continuous reaction was carried out under the conditions of temperature 60°C, pressure 3MPa (gauge pressure), and residence time 9 minutes, wherein 0.3g of the catalyst G was placed in a 0.5L autoclave, and supplied thereto at a rate of 500mL/min Nitrogen, propylene was supplied at a rate of 2162mmol/Hr, water/ _acetonitrile (weight ratio = water/acetonitrile = 20/80) with 7wt% _H2O2 was supplied at a rate of 633mL/Hr, and the reaction mixture was passed through a filter at the same time from the Remove from the autoclave. The liquid and gas phases taken out after 2 hours of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 516 mmol/Hr, propylene glycol was produced at a yield of 0.72 mmol/Hr, and the conversion rate of hydrogen peroxide was 69.8%.

Example 13

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst H was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 652 mmol/Hr, propylene glycol was produced at a yield of 3.96 mmol/Hr, and the conversion rate of hydrogen peroxide was 88.3%.

Example 14

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst I was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 695 mmol/Hr, propylene glycol was produced at a yield of 3.79 mmol/Hr, and the conversion rate of hydrogen peroxide was 96.4%.

Example 15

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst J was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 495 mmol/Hr, propylene glycol was produced at a yield of 0.87 mmol/Hr, and the conversion rate of hydrogen peroxide was 65.7%.

Example 16

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst K was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 485 mmol/Hr, propylene glycol was produced at a yield of 0.51 mmol/Hr, and the conversion rate of hydrogen peroxide was 65.2%.

Example 17

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst L was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 535 mmol/Hr, propylene glycol was produced at a yield of 0.48 mmol/Hr, and the conversion rate of hydrogen peroxide was 71.8%.

Example 18

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst M was used instead of the catalyst G. The liquid and gas phases taken out after 1 hour of reaction were analyzed by gas chromatography, and it was determined that propylene oxide was produced at a yield of 522 mmol/Hr, propylene glycol was produced at a yield of 0.56 mmol/Hr, and the conversion rate of hydrogen peroxide was 71.5%.

Comparative Example 6

Propylene oxide was prepared in the same steps as in Example 12 except that the catalyst M was used instead of the catalyst G. The liquid phase and gas phase taken out after the reaction for 1 hour were analyzed by gas chromatography, and it was confirmed that propylene oxide was produced at a yield of 522 mmol/Hr, and propylene glycol was produced at a yield of 0.56 mmol/Hr, and the conversion rate of hydrogen peroxide was 71.5%.

When used in Examples 19-21 and Comparative Examples 7-9 described below, all catalysts were contacted with hydrogen peroxide prior to reaction as described below. The catalyst was placed in a water/acetonitrile (1/4 (weight ratio)) solution containing 0.1 wt% hydrogen peroxide at a temperature of 25°C for 1 hour at a ratio of 100 g of the solution to 0.266 g of the catalyst. After filtering the solution containing the catalyst, the collected catalyst was washed with 500 mL of water.

Example 19

The continuous reaction was carried out under the conditions of temperature 60°C, pressure 0.8 MPa (gauge pressure), and residence time 90 minutes, wherein 0.266 g of the catalyst A previously treated with hydrogen peroxide and 0.03 g of the Pd/AC were placed in 0.5L autoclave, and will contain propylene/oxygen/hydrogen/nitrogen source with a volume ratio of 4/4/10/82 and water/acetonitrile (=20/80 , weight ratio) solutions were supplied thereto at a rate of 16 L/hr and 108 mL/hr, respectively, while the reaction mixture was taken out from the autoclave through a filter. The liquid and gas phases taken out after 5 hours of reaction were analyzed by gas chromatography, and the selectivity of propylene oxide and propylene glycol produced at a yield of 6.60 mmol/Hr was 6.5%.

Example 20

Propylene oxide was prepared in the same steps as in Example 19, except that the catalyst B was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was confirmed that propylene oxide was produced at a yield of 6.27 mmol/Hr, and the selectivity of propylene glycol was 3.7%.

Example 21

Propylene oxide was prepared in the same steps as in Example 19, except that the catalyst D was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that the selectivity of propylene oxide and propylene glycol produced at a yield of 7.19 mmol/Hr was 9.7%.

Comparative Example 7

Propylene oxide was prepared in the same steps as in Example 19, except that the solid product 1 was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that the selectivity of propylene oxide and propylene glycol produced at a yield of 5.64 mmol/Hr was 9.3%.

Comparative Example 8

Propylene oxide was prepared using the same procedure as in Example 19, except that the solid product 3 was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was confirmed that propylene oxide was produced at a yield of 5.56 mmol/Hr, and the selectivity of propylene glycol was 10.6%.

Comparative Example 9

Propylene oxide was prepared in the same steps as in Example 19, except that the solid product 4 was used instead of the catalyst A. The liquid and gas phases taken out after 6 hours of reaction were analyzed by gas chromatography, and it was determined that the selectivity of propylene oxide and propylene glycol produced at a yield of 3.59 mmol/Hr was 8.9%.

When used in Examples 22-25 below, all catalysts were treated with hydrogen peroxide prior to reaction as described below. The catalyst was placed in a water/acetonitrile (1/4 (weight ratio)) solution containing 0.1 wt% hydrogen peroxide at a temperature of 25° C. at a ratio of 100 g solution to 0.05 g catalyst for 1 hour. After filtering the solution containing the catalyst, the collected catalyst was washed with 500 mL of water. The catalyst thus washed was further vacuum-dried at 150° C. for 1 hour, and then reacted.

Example 22

A 30% H ₂ O ₂ aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.), acetonitrile, and ion-exchanged water was used to prepare a solution of 0.5 wt % H ₂ O ₂ , 19.9 wt % water, and 79.6 wt % acetonitrile. 60 g of the prepared solution and 0.010 g of the catalyst A previously treated with hydrogen peroxide were placed in a 100 mL stainless steel autoclave. Next, the autoclave was transferred to an ice bath, and 1.2 g of liquid propylene was charged thereinto. The pressure of the reaction system was further increased to 2 MPa-G using argon. The autoclave was placed in a hot water bath at 60°C and removed from the hot water bath after 1 hour. Samples were taken and analyzed using gas chromatography. As a result, 4.51 mmol of propylene oxide was produced.

Example 23

Propylene oxide was prepared in the same procedure as in Example 22 except that benzonitrile was used instead of acetonitrile. 5.66 mmol of propylene oxide are produced.

Example 24

Propylene oxide was prepared by the same procedure as in Example 22 except that tert-butanol was used instead of acetonitrile. 8.06 mmol of propylene oxide are produced.

Example 25

Propylene oxide was prepared in the same procedure as in Example 22, except that methanol was used instead of acetonitrile. 2.27 mmol of propylene oxide were produced.

Industrial applicability

The preparation method of the present invention can prepare oxidized compounds with high yield and high selectivity, and thus has industrial applications. The titanosilicate (I) is used as a catalyst in the production process.

Claims (19)

1. A process for the preparation of an oxidized compound comprising reacting an organic compound with an oxidizing agent in the presence of titanosilicate (I) or its silylated form by making titanosilicate obtained by contacting a salt (II) with a structure directing agent, said titanosilicate (II) having an X-ray diffraction pattern in the form of the following interplanar distance d: 1.24±0.08 nm, 1.08±0.03 nm, 0.9±0.03 nm, 0.6±0.03 nm, 0.39±0.01 nm and 0.34±0.01nm. 2. The method for producing an oxygenated compound according to claim 1, wherein the organic compound is an olefinic compound or an aromatic compound. 3. The method for producing an oxidizing compound according to claim 1, wherein the molar ratio of silicon to nitrogen (Si/N ratio) of the titanosilicate (I) is 5-20 inclusive. 4. The method for preparing oxidized compounds according to claim 1, wherein the ratio of the specific surface area (SH ₂ O) to the specific surface area (SN ₂ ) of the titanosilicate (I) (SH ₂ O/SN ₂ ) 0.7-1.5 (inclusive), the specific surface areas SH ₂ O and SN ₂ were measured by water vapor adsorption and nitrogen adsorption methods, respectively. 5. The method for preparing oxidized compounds according to claim 1, wherein the titanosilicate (II) is a crystalline titanosilicate having a MWW or MSE structure or a Ti-MWW precursor (a). 6. The method for preparing oxidized compounds according to claim 1, wherein the structure directing agent is piperidine or hexamethyleneimine or a mixture thereof. 7. The method for preparing an oxidized compound according to claim 1, wherein the contacting of the titanosilicate (II) with the structure directing agent is performed at a temperature of 0-250°C. 8. A titanosilicate or a silylated form thereof, wherein said titanosilicate has a silicon to nitrogen molar ratio (Si/N ratio) of 10-20 inclusive. 9. A titanosilicate or a silylated form thereof according to claim 8, wherein said titanosilicate is obtained by contacting titanosilicate (II) with a structure directing agent, said titanosilicate (II) have an X-ray diffraction pattern in the form of the following interplanar distance d: 1.24±0.08 nm, 1.08±0.03 nm, 0.9±0.03 nm, 0.6±0.03 nm, 0.39±0.01 nm and 0.34±0.01nm. 10. The titanosilicate or silylated form thereof according to claim 9, wherein the titanosilicate (II) is a crystalline titanosilicate having a MWW or MSE structure or a Ti-MWW precursor ( a). 11. Use of a titanosilicate or a silylated form thereof according to claim 8 as a catalyst in a process for the preparation of oxidized compounds. 12. Catalysts for oxidation reactions of organic compounds comprising titanosilicates (I) or silylated forms thereof obtained by combining titanosilicates (II) with structure-directed The titanosilicate (II) has an X-ray diffraction pattern expressed in the form of the following interplanar distance d: 1.24±0.08 nm, 1.08±0.03 nm, 0.9±0.03 nm, 0.6±0.03 nm, 0.39±0.01 nm and 0.34±0.01nm. 13. The method for preparing an oxidized compound according to claim 1, wherein the oxidizing agent is oxygen or a peroxide. 14. The method for preparing an oxidized compound according to claim 13, wherein the peroxide is at least one compound selected from the group consisting of hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide , cumene hydroperoxide, methylcyclohexyl hydroperoxide, tetralin hydroperoxide, isobutylbenzene hydroperoxide, ethylnaphthalene hydroperoxide and peracetic acid. 15. The method for preparing an oxidized compound according to claim 1, wherein the reaction is an epoxidation reaction of an olefinic compound or a hydroxylation reaction of a benzene or phenolic compound. 16. The method for preparing an oxidized compound according to claim 1, wherein the reaction is an epoxidation reaction of an olefinic compound, and the oxidizing agent is hydrogen peroxide. 17. The method for producing an oxidized compound according to claim 16, wherein the oxidizing agent is hydrogen peroxide synthesized in the same reaction system as that of the epoxidation reaction of the olefin compound. 18. The process for the preparation of oxidized compounds according to claim 1, wherein the reaction is carried out in the presence of an organic solvent selected from the group consisting of alcohols, ketones, nitriles, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons , esters and mixtures thereof. 19. The method for preparing oxygenated compounds according to claim 18, wherein the organic solvent is acetonitrile or tert-butanol.

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